EP0417971A2

EP0417971A2 - Method of cleaning surfaces

Info

Publication number: EP0417971A2
Application number: EP90309727A
Authority: EP
Inventors: Richard Charles Chromecek; Milan Franz Sojka
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 1989-09-14
Filing date: 1990-09-05
Publication date: 1991-03-20
Also published as: AU629040B2; KR910021267A; EP0417971A3; AU6244390A; US5037485A; JPH03188982A; CA2024603A1

Abstract

This invention relates to a process of cleaning a surface soiled with a staining agent. The method includes the steps of aplying to the soiled surface a highly cross-linked macroporous hydrophobic copolymer which contains a chemical entrapped therein which is a solvent for the staining agent present on the soiled surface, dissolving the staining agent with the solvent, absorbing the staining agent into the solvent entrapped copolymer and removing the copolymer containing the solvent and the dissolved staining agent from the surface.

Description

This invention relates to a process of cleaning a surface soiled with a staining agent. The method includes the steps of applying to the soiled surface a highly cross-linked macroporous hydrophobic copolymer which contains a chemical entrapped therein which is a solvent for the staining agent present on the soiled surface, dissolving the staining agent with the solvent, absorbing the staining agent into the solvent entrapped copolymer and removing the copolymer containing the solvent and the dissolved staining agent from the surface.
In certain of the more specific embodiments of the present invention, one monomer of the copolymer is a monounsaturated monomer and the monounsaturated monomer is lauryl methacrylate. One monomer of the copolymer can also be a polyunsaturated monomer and the polyunsaturated monomer is selected from the group consisting of ethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
The copolymer is in the form of a powder and the powder is a combined system of particles, the system of particles including unit particles of less than about one micron in average diameter, agglomerates of fused unit particles of sizes in the range of about twenty to eighty microns in average diameter and aggregates of clusters of fused agglomerates of sizes in the range of about two-hundred to about twelve-hundred microns in average diameter. The soiled surface can be a textile in which case the copolymer containing the solvent is pressed and rubbed into the textile surface after being applied to the surface. The solvent is evaporated from the copolymer following removal of the copolymer containing the solvent and the staining agent from the surface and the solvent free copolymer containing the staining agent is discarded.
The copolymer containing the solvent and the staining agent can be removed from the surface by brushing the surface, followed by the application of pressurized air to the brushed surface. The staining agent may be butter, grass and motor oil and the soiled surface treated in accordance with the present invention could be wool, paper, cotton, silk, rayon, linen and polyester. The solvent is preferably heptane, methylene chloride and ethyl alcohol, although other appropriate solvents may be employed.
The invention is also directed to a more simplified process in which no solvent is employed. In this case, the steps are related to a process of cleaning a surface soiled with a staining agent by applying to the soiled surface a highly cross-linked macroporous hydrophobic copolymer, rubbing and mixing the copolymer into the staining agent on the soiled surface, absorbing the staining agent into the copolymer and removing the copolymer containing the staining agent from the surface. The staining agent is, for example, grease, lipid deposits and plaque, while the soiled surface may be glass, spectacle lenses and dentures. The copolymer containing the staining agent is removed from the surface by flushing the surface with water.
A precipitation polymerization process is used for producing the macroporous cross-linked copolymer. In the process, there is copolymerized at least one monounsaturated monomer and at least one polyunsaturated monomer in the presence of an organic liquid which is a solvent for and dissolves the monomers but not the copolymer. The copolymerization of the monomers is initiated by means of a free radical generating catalytic compound, precipitating a copolymer in the solvent in the form of a powder. A dry powder is formed by removing the solvent from the precipitated copolymeric powder.
The solvent is preferably isopropyl alcohol, although ethanol, toluene, heptane, xylene, hexane, ethyl alcohol and cyclohexane may also be employed. The monounsaturated monomer and the polyunsaturated monomer can be present in mol ratios of, for example, 20:80, 30:70, 40:60 or 50:50. The process includes the step of stirring the monomers, solvent and the free radical generating catalytic compound, during copolymerization. Preferably, the dry powder is formed by filtering excess solvent from the precipitated powder and the filtered powder is vacuum dried. The powder may then be "post adsorbed" with various functional materials.
The powders of the present invention may be used as carriers or adsorbents for materials such as water, aqueous systems, emollients, moisturizers, fragrances, dyes, pigments, flavors, drugs such as ibuprofen, phosphoric acid, insect repellents, vitamins, sunscreens, detergents, cosmetics, pesticides, pheromones, herbicides, steroids, sweeteners, pharmaceuticals and antimicrobial agents. Finely divided solids such as analgesic materials can be adsorbed by dissolving the finely divided analgesic in a solvent, mixing the analgesic and solvent with the powder and removing the solvent. Other post adsorbable materials include alkanes, alcohols, acid esters, silicones, glycols, organic acids, waxes and alcohol ethers.
These and other objects, features and advantages, of the present invention will become apparent when considered in light of the following detailed description, including the accompanying drawings.

Figure 1 of the drawings is a photomicrograph of the various components of the complex structure of the powder produced in Example I and including unit particles, agglomeratures and aggregates.
Figures 2 and 3 are photomicrographs of the agglomerates and aggregates of Figure 1, respectively, shown on a larger scale.
Figure 4 is a photomicrograph of a polymer bead produced by suspension polymerization.
Figure 5 is a photomicrograph of the bead of Figure 4 with a portion of the shell removed to reveal the interior structure of the bead.
Figure 6 is a photomicrograph of a copolymeric powder material. The powder is shown in magnification as it appears when the agitation rate employed in the process for producing the powder is zero rpm.
Figures 7-10 are additional photomicrographs of copolymeric powder materials. The powder is shown in magnification as it appears when the agitation rate employed in the process for producing the powder varies from seventy-five rpm up to eight hundred rpm.

In the above figures in the drawings, the magnification is indicated in each instance. For example, the magnification in Figures 6-9 is 1000X and 2000X in Figure 10. Figures 6-10 also include an insert identifying a length approximating ten microns for comparative purposes.
It should be pointed out, that in viewing the various figures, one will note that as the rate of stirring is increased from zero rpm up to eight hundred rpm, that the size of the unit particles increase. This is in direct opposition to what has been traditionally observed in suspension polymerization systems, wherein increases in stirring rates decrease particle size. Because of the increased size of the unit particles shown in Figure 10 and the resulting decrease in surface area, the adsorptive capacity of these large particles is less than the adsorptive capacity of the smaller sized particles shown in Figures 6-9.
The most effective unit particles can be produced if the rate of stirring is maintained below about three hundred rpm, although particles produced at rates beyond three hundred rpm are useful and adsorptive, but to a lesser extent.
The material of the present invention, can be broadly and generally described as a crosslinked copolymer capable of entrapping solids, liquids and gases. The copolymer is in particulate form and constitutes free flowing discrete solid particles even when loaded with an active material. When loaded, it may contain a predetermined quantity of the active material. One copolymer of the invention has the structural formula:
where the ratio of x to y is 80:20, R′ is CH₂CH₂ and R˝ is -(CH₂)₁₁CH₃.
The copolymer is highly crosslinked as evidenced by the foregoing structural formula and is more particularly a highly crosslinked polymethacrylate copolymer. This material is manufactured by the Dow Corning Corporation, Midland, Michigan, U.S.A. and sold under the trademark POLYTRAP®. It is a low density, highly porous, free-flowing white particulate and the particles are capable of adsorbing high levels of lipophilic liquids and some hydrophilic liquids, while at the same time maintaining a free-flowing particulate character.
In the powder form, the structure of the particulate is complex and consists of unit particles less than one micron in average diameter. The unit particles are fused into agglomerates of twenty to eighty microns in average diameter. These agglomerates are loosely clustered into macro-particles termed aggregates of about 200 to about 1200 microns in average diameter.
Adsorption of actives to form post adsorbent powder, can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active ingredient is added to the empty dry powder and the spoon is used to gently fold the active into the powder. Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel containing the powder and tumbling the materials until a consistency is achieved. More elaborate blending equipment such as ribbon or twin cone blenders can also be employed.
The following example illustrates the method for making a post adsorbent powder, of the type illustrated in Figures 1-3 and 6-10.

Example I

A hydrophobic porous copolymer was produced by the precipitation polymerization technique by mixing in a five hundred milliliter polymerization reactor equipped with a paddle type stirrer, 13.63 grams of ethylene glycol dimethacrylate monomer or eighty mole percent and 4.37 grams of lauryl methacrylate monomer or twency mole percent. Isopropyl alcohol was added to the reactor as the solvent in the amount of 282 grams. The monomers were soluble in the solvent, but not the precipitated copolymer. The process can be conducted with only polyunsaturated monomers if desired. The mixture including monomers, solvent and 0.36 grams of catalytic initiator benzoyl peroxide, was purged with nitrogen. The system was heated by a water bath to about 60°C. until copolymerization was initiated, at which time, the temperature was increased to about 70-75°C. for six hours, in order to complete the copolymerization. During this time, the copolymer precipitated from the solution. The copolymerization produced unit particles of a diameter less than about one micron. Some of the unit particles adhered together providing agglomerates of the order of magnitude of about twenty to eighty microns in diameter. Some of the agglomerates adhered further and were fused and welded one to another, forming aggregates of loosely held assemblies of agglomerates of the order of magnitude of about two to eight hundred microns in diameter. The mixture was filtered to remove excess solvent and a wet powder cake was tray dried in a vacuum oven. A dry hydrophobic copolymeric powder consisting of unit particles, agglomerates and aggregates was isolated.

The adsorptive capacity of the hydrophobic particulates produced in Example I, as a function of the stirring rate, was determined. The stirring rate during the reaction in Example I significantly influenced the adsorption properties of the particulate materials. The adsorptivity of the particulate materials decreases with an increase in stirring rate and the density of the particulates increases. These results are set forth in Tables I-III.

TABLE I

Agitation Rate (RPM)	Bulk Density Size (g/cc)	Average Aggregate Size (µ)	Average Agglomerate Size (µ)	Average Unit Particle Size (µ)	Adsorption Capacity*
0	0.067	182.5	33.9	1.0	83.0
75	0.077	140.6	36.6	0.5	84.8
150	0.071	149.8	39.8	0.8	83.0
300	0.293	47.0	34.0	1.5-2.0	58.3
800	0.440	--	10.0	3.0-5.0	37.7

* = Percent Silicone Oil

TABLE II

		Adsorption Capacity %
Stirring Speed RPM	Water	Mineral Oil	Glycerine	Organic Ester*
0	0	80	75	80
75	0	83.9	75	81.5
150	0	80	75	80
300	0	54.5	58.3	54.5

* = 2-ethylhexyl-oxystearate

TABLE III

	Adsorption Capacity %			Density (g/cm³)
RPM	Mineral Oil	2-ethylhexyl oxystearate	Silicone Oil	Bulk	Tapped
0	82.5	82.5	86.5	0.0368	0.0580
75	82.3	82.2	86.5	0.0462	0.0667
150	82.3	82.3	86.3	0.0527	0.0737
200	81.5	81.5	85.7	0.0554	0.0752
250	79.2	80.0	84.8	0.0636	0.0859
300	68.8	68.8	75.0	0.1300	0.1768
450	58.3	58.3	61.5	0.1736	0.2392
600	54.5	54.5	60	0.1933	0.2792
700	42.2	42.5	45.7	0.2778	0.4142
800	33.3	28.6	33.3	0.3862	0.5322
1000	32.8	28.5	32.9	0.3808	0.5261

In the foregoing tables, it can be seen that adsorption and density, as a function of stirring rate, was determined for several fluids including a silicone oil, water, mineral oil, glycerine and an organic ester. From zero rpm up to about 250 rpm, the adsorptivity of the porous copolymeric powder particulates of Example I remained essentially consistent. However, at about three hundred rpm, there was a substantial decrease in adsorptivity, which decrease became more apparent as the stirring rate was increased up to about one thousand rpm. A similar pattern is evidenced by the data which are reflective of the density.
This phenomenon is more apparent in the photomicrographic figures of the drawing. Thus, it can be seen from Figure 6, that the particle size of the unit particles increases as the stirring rate is increased, as evidenced by Figure 10. A progression in this phenomenon can be observed in Figures 7-9.
While the procedure of Example I is a precipitation polymerization process and not a suspension polymerization system, the prior art dealing with suspension polymerization processes, teaches that an increase in stirring rate causes a decrease in particle size. This is documented, for example, in U.S. Patent No. 4,224,415, issued September 23, 1980, and in the PCT International Publication. The PCT International Publication employs stirring rates upwards of nine hundred to twelve hundred rpm. In Example I of the present invention, however, increases in stirring rates not only did not decrease the particle size, but in fact had exactly the opposite effect, causing the unit particle size to increase. As the rate of stirring increased from zero rpm up to one thousand, the density of the particles increased and the adsorptive capacity decreased.
In accordance with the above, it is possible to tailor porous adsorbent powders of a particular particle size and adsorptivity by means of stirring rate. Thus, with large unit particles in Figure 10, the adsorptive capacity is less than the adsorptive capacity of smaller sized unit particles in Figures 6-9. While the most effective particles are produced when the rate of stirring is maintained below about three hundred rpm, particles produced at rates beyond three hundred rpm are useful.
It is important to understand that the method of Example I for the production of porous copolymer particulate powder materials is characterized as a precipitation polymerization technique. In accordance with the technique, monomers are dissolved in a compatible volatile solvent in which both monomers are soluble. Polymer in the form of a powder is precipitated and the polymer is insoluble in the solvent. No surfactant or dispersing aid is required. The materials produced are powders and not spheres or beads. The powder particulates include unit particles, agglomerates and aggregates. The volatile solvent is subsequently removed resulting in a dry powder, which can be post adsorbed with a variety of functional active ingredients. The suspension polymerization process on the other hand, provides that polymerization be carried out in water and in some cases chloroform or chlorinated solvents. The monomers, the active and the catalyst form beads or droplets in water and polymerization occurs within each bead. A surfactant or stabilizer, such as polyvinyl pyrrolidone, is required in order to prevent the individually formed beads and droplets from coalescing. The resulting beads, with the active material entrapped therein, include a substantially spherical outer crust or shell, the interior of which contains a macroporous structure of fused unit particles, agglomerates and aggregates. The bead is about ten microns in average diameter to about one hundred-fifty microns, depending upon the rate of agitation employed during the process. Such beads are shown in Figures 4 and 5 and the process is set forth in Example III.
Some unique features of the powders of Example I and Figures 1-3 and 6-10 are their ability to adsorb from sixty to eighty percent of a liquid and yet remain free flowing. The materials provide a regulated release of volatile ingredients such as cyclomethicone entrapped therein and have the capability of functioning as carriers for other non-volatile oils. Loaded powders disappear when rubbed upon a surface. This phenomenon is believed due to the fact that large aggregates of the material scatter light rendering the appearance of a white particulate, however, upon rubbing, these large aggregates decrease in size approaching the range of visible light and hence seem to disappear. The materials find applications in diverse areas such as cosmetics and toiletries, household and industrial products, pesticides, pheromone carriers and pharmaceuticals. The materials do not swell in common solvents and are capable of physically adsorbing active ingredients by the filling of interstitial voids by capillary action. The active ingredients are subsequently released by capillary action or wicking from the voids within the particulates.
The following example illustrates a precipitation polymerization process in which an organic ester is entrapped "in situ" in the polymer powder.

Example II

7 grams of 2-ethylhexyl oxystearate was mixed with 1.5 grams of ethylene glycol dimethacrylate and 1.5 grams of lauryl methacrylate in a glass test tube. The solution was deaerated for five (5) minutes and 0.1 ml of t-butyl peroctoate was added and mixed while heating to 80°C. in an oil bath. After 20 minutes, the contents solidified and the mixture was maintained at about 80°C. for an additional hour to assure full polymerization. A semi-soft, heterogeneous white opaque polymer mass resulted containing the entrapped ester.
The powder of Example II differs from the powder of Example I in that the solvent in Example I is removed resulting in a dry empty powder which is post adsorbed with other functional materials. The powder of Example II is otherwise similar to the material shown in Figures 1-3.
Example III illustrates a process for the production of beads as shown in Figures 4 and 5. The process is suspension polymerization and an organic ester is entrapped "in situ".

Example III

1.20 grams of polyvinyl pyrrolidone was dissolved in 1500 ml of water in a 2000 ml three necked resin flask equipped with a stirrer, thermometer and nitrogen purge. solution of 335 grams of 2-ethylhexyl oxystearate, 132 grams ethylene glycol dimethacrylate, 33 grams 2-ethylhexyl methacrylate and 5 ml t-butyl peroctoate, was bubbled with nitrogen for 5 minutes. The resultant mix was slowly added to the stirred aqueous solution of polyvinyl pyrrolidone at 22°C. under nitrogen. The temperature was raised to 80°C. with constant agitation and held until polymerization started in approximately 15 minutes and maintained at 80°C. for an additional 2 hours to complete the reaction. Semi-soft, white opaque beads were collected by filtering off the supernatant liquid and dried to remove any excess water. The beads weighed 450 g for a yield of 90% and were 0.25 to 0.5 mm in diameter. Other protective colloids such as starch, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose or inorganic systems such as divalent alkali metal hydroxides, for example MgOH, may be used in place of the polyvinyl pyrrolidone suspending medium.
In Example III macroporous polymers submicron in size are produced with two or more monomers, at least one monomer of which contains more than a single double bond. The polymerization is conducted in the presence of an active ingredient which does not dissolve or swell the resulting polymer. The monomers and the active ingredient are mutually soluble, but are insoluble in the aqueous suspending medium in which droplets are formed. Polymerization occurs within suspended droplets and beads or spheres are produced. The active ingredient which is polymerized "in situ" is entrapped and contained within the beads, but the active ingredient is capable of being released. It is also possible to use a volatile liquid during polymerization and to subsequently thermally drive off the volatile liquid, leaving behind a porous polymer bead product into which a variety of active materials can be subsequently adsorbed.
Examples of polyunsaturated monomers suitable for use in accordance with the present invention are ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol propane ethoxylated triacrylate, ditrimethylol propane dimethacrylate; propylene, dipropylene and higher propylene glycols, 1,3 butylene glycol dimethacrylate, 1,4 butanediol dimethacrylate, 1,6 hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, dipentaerythritol dimethacrylate, bisphenol A dimethacrylate, divinyl and trivinyl benzene, divinyl and trivinyl toluene triallyl maleate, triallyl phosphate, diallyl maleate, diallyl itaconate and allyl methacrylate. The monounsaturated monomers include allyl methacrylates and acrylates having straight or branched chain alkyl groups with 1 to 30 carbon atoms, preferably 5 to 18 carbon atoms. Preferred monomers include lauryl methacrylate, 2-ethylhexyl methacrylate, isodecylmethacrylate, stearyl methacrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, diacetone acrylamide, phenoxy ethyl methacrylate, tetrahydrofurfuryl methacrylate and methoxy ethyl methacrylate.
As noted previously, the copolymer can be formed by copolymerizing one monounsaturated monomer with one polyunsaturated monomer or with only polyunsaturated monomers.

Example IV

Example I was repeated for each of a series of monomer systems shown in Tables IV-XVII. In each instance, submicron sized copolymeric powders were produced employing a stirring speed of about seventy-five RPM. The catalyst was benzoyl peroxide. Adsorption capacities of the various copolymeric powders for fluids were determined and are shown in the Tables, along with the mole ratios of monomers and the solvent. The abbreviations used in Tables IV-XVII are identified as follows:

DAA	Diacetone acrylamide
EGDM	Ethylene glycol dimethacrylate
TEGDM	Tetraethylene glycol dimethacrylate
ST	Styrene
DVB	Divinylbenzene
VP	Vinyl pyrrolidone
IBOMA	Isobornyl methacrylate
PEMA	Phenoxyethyl methacrylate
IDMA	Isodecyl methacrylate
STMA	Stearyl methacrylate
HPMA	Hydroxypropyl methacrylate
CYMA	Cyclohexyl methacrylate
DMAEMA	Dimethylaminoethyl methacrylate
TBAEMA	t-butyl aminoethyl methacrylate
AMPS	2-acrylamido propane sulfonic acid
BMA	Butyl methacrylate
EHMA	2-ethylhexyl methacrylate
MMA	Methyl methacrylate
HEMA	2-hydroxyethyl methacrylate
EHO	2-ethylhexyl oxystearate
GG	Glucose glutamate
IPA	Isopropyl alcohol
PEG	Polyethylene glycol 200

TABLE IV

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	GG	Water
DAA/EGDM	20/80	Xylene	75	82	83	78
DAA/EGDM	30/70	Xylene	77	80	83	78
DAA/EGDM	40/60	Xylene	75	75	83	77
DAA/EGDM	50/50	Xylene	50	57	67	0
DAA/EGDM	60/40	Xylene	40	40	50	0
DAA/TEGDM	20/80	Xylene	40	50	62	58
DAA/TEGDM	30/70	Xylene	29	40	50	55
DAA/TEGDM	40/60	Xylene	25	28	40	43
DAA/TEGDM	50/50	Xylene	25	30	40	43
DAA/TEGDM	60/40	Xylene	22	29	40	40

TABLE V

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	PEG	Water
ST/TEGDM	20/80	IPA	58	69	69	67
ST/TEGDM	30/70	IPA	58	64	67	69
ST/TEGDM	40/60	IPA	62	71	71	61
ST/TEGDM	50/50	IPA	67	62	54	58
ST/TEGDM	60/40	IPA	50	58	58	54
ST/TEGDM	70/30	IPA	50	58	50	54
ST/TEGDM	80/20	IPA	44	54	50	50
ST/DVB	20/80	IPA	80	75	75	0
ST/DVB	30/70	IPA	75	67	75	0
ST/DVB	40/60	IPA	69	67	67	0
ST/DVB	50/50	IPA	64	72	67	0
ST/DVB	60/40	IPA	67	71	71	0
ST/DVB	70/30	IPA	71	75	76	0
ST/DVB	80/20	IPA	50	50	50	0

TABLE VI

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	GG	Water
VP/EGDM	20/80	Xylene	77	80	74	73.6
VP/EGDM	30/70	Xylene	76	79	78.3	70
VP/EGDM	40/60	Xylene	70	67	75.6	75
VP/EGDM	50/50	Xylene	72	76	80	76
VP/EGDM	60/40	Xylene	74	80	76	77
VP/EGDM	70/30	IPA	71	78	74	75
VP/EGDM	80/20	IPA	67	75	73	74
VP/TEGDM	20/80	Xylene	58	68.8	61.5	67.7
VP/TEGDM	30/70	Xylene	70	67	54.5	68.8
VP/TEGDM	40/60	Xylene	54.5	61.5	52.4	64.3
VP/TEGDM	50/50	Xylene	44.4	47.4	52.4	52.4
VP/TEGDM	60/40	Xylene	50	44.4	50	54.4
VP/TEGDM	70/30	Xylene	50	47.4	44.4	50
VP/TEGDM	80/20	Xylene	54.5	52.4	60	58

TABLE VII

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	GG	Water
IBOMA/EGDM	20/80	IPA	62.9	9.1	71.4	0
IBOMA/EGDM	30/70	IPA	64.3	16.6	67.7	0
IBOMA/EGDM	40/60	IPA	68.7	28.6	61.5	0
IBOMA/EGDM	50/50	IPA	67.7	16.7	58.3	0
IBOMA/EGDM	60/40	IPA	50	23.1	50	0
IBOMA/EGDM	70/30	IPA	50	9.1	47.3	0
IBOMA/EGDM	80/20	IPA	52.3	16.6	44.4	0
IBOMA/TEGDM	20/80	IPA	66.6	62.9	61.5	0
IBOMA/TEGDM	30/70	IPA	61.5	61.5	70.6	0
IBOMA/TEGDM	40/60	IPA	64.3	64.3	71.4	0
IBOMA/TEGDM	50/50	IPA	61.5	66.6	67.7	0
IBOMA/TEGDM	60/40	IPA	58.3	54.5	54.5	0
IBOMA/TEGDM	70/30	IPA	47.3	50	41.1	0
IBOMA/TEGDM	80/20	IPA	37.5	41.1	33.3	0

TABLE VIII

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	GG	Water
PEMA/EGDM	20/80	IPA	64.3	68.7	66.6	61.5
PEMA/EGDM	30/70	IPA	54.5	50	54.5	44.4
PEMA/EGDM	40/60	IPA	52.3	47.3	72.2	9
PEMA/EGDM	50/50	IPA	54.5	33.3	62.9	0
PEMA/EGDM	60/40	IPA	67.7	28.5	70.5	0
PEMA/EGDM	70/30	IPA	69.7	44.4	60.7	0
PEMA/EGDM	80/20	IPA	66.6	68.7	66.6	0
PEMA/TEGDM	20/80	IPA	58.3	56.5	66.6	58.3
PEMA/TEGDM	30/70	IPA	64.2	70.5	67.7	62.9
PEMA/TEGDM	40/60	IPA	66.6	67.7	71.4	69.7
PEMA/TEGDM	50/50	IPA	66.6	70.5	73.6	72.2
PEMA/TEGDM	60/40	IPA	58.3	62.9	52.3	61.5
PEMA/TEGDM	70/30	IPA	50	58.3	52.3	54.5
PEMA/TEGDM	80/20	IPA	67.7	73.6	76.1	47.3

TABLE IX

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	PEG	Water
IDMA/EGDM	20/80	IPA	55	64	70	0
IDMA/EGDM	30/70	IPA	38	50	44	0
IDMA/EGDM	40/60	IPA	50	67	69	0
IDMA/EGDM	50/50	IPA	58	64	67	0
IDMA/EGDM	60/40	IPA	58	69	69	0
IDMA/TEGDM	20/80	IPA	62	70	70	0
IDMA/TEGDM	30/70	IPA	50	62	62	0
IDMA/TEGDM	40/60	IPA	62	67	67	0
IDMA/TEGDM	50/50	IPA	38	44	50	0
IDMA/TEGDM	60/40	IPA	38	55	50	0

TABLE X

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	PEG	Water
STMA/EGDM	10/90	IPA	66	64.3	66.7	0
STMA/EGDM	20/80	IPA	69	63	65.5	0
STMA/EGDM	30/70	IPA	73-75	58.3	61.5	0
STMA/EGDM	40/60	IPA	69-71	54.5	58.3	0
STMA/EGDM	50/50	IPA	60-63	52.4	52.4	0
STMA/TEGDM	20/80	IPA	50	47.4	52.4	0
STMA/TEGDM	30/70	IPA	50	64.3	50	0
STMA/TEGDM	40/60	IPA	52.4	61.5	58.3	0
STMA/TEGDM	50/50	IPA	47.4	52.4	65.5	0

TABLE XI

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	PEG	Water
HPMA/EGDM	20/80	Xylene	64.3	61.5	61.5	9
HPMA/EGDM	30/70	Xylene	54.5	16.7	58.3	0
HPMA/EGDM	40/60	Xylene	54.5	9	58.3	0
HPMA/EGDM	50/50	Xylene	37.5	58.3	50	0
HPMA/EGDM	60/40	Xylene	44.4	61.5	58.3	0
HPMA/EGDM	70/30	Xylene	50	44.4	37.5	0
HPMA/EGDM	80/20	Xylene	61.5	16.7	58.3	0
HPMA/TEGDM	20/80	Xylene	50	58.3	54.5	61.5
HPMA/TEGDM	30/70	Xylene	56.5	54.5	50	60
HPMA/TEGDM	40/60	Xylene	50	58.3	52.4	54.5
HPMA/TEGDM	50/50	Xylene	52.4	61.5	54.5	56.5
HPMA/TEGDM	60/40	Xylene	33.3	47.4	44.4	54.5
HPMA/TEGDM	70/30	Xylene	54.5	44.4	54.5	50
HPMA/TEGDM	80/20	Xylene	50	47.4	41.2	37.5

TABLE XII

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	EHO	Glycerine	PEG	Water
CYMA/EGDM	80/20	IPA	61.5	71.4	66.6	0
CYMA/EGDM	70/30	IPA	60	66	64.2	0
CYMA/EGDM	60/40	IPA	61.5	66	66.6	0
CYMA/EGDM	50/50	IPA	64.2	66	68.7	0
CYMA/EGDM	40/60	IPA	64.2	66	68.7	0
CYMA/EGDM	30/70	IPA	61.5	66	66.6	0
CYMA/EGDM	20/80	IPA	66.6	71.4	75	61.5
CYMA/TEGDM	80/20	IPA	68.7	0	68.7	0
CYMA/TEGDM	70/30	IPA	71.4	0	69.7	0
CYMA/TEGDM	60/40	IPA	66.6	0	62.9	0
CYMA/TEGDM	50/50	IPA		0		0
CYMA/TEGDM	40/60	IPA	60	0	72.9	0
CYMA/TEGDM	30/70	IPA	64.2	0	72.2	0
CYMA/TEGDM	20/80	IPA	61.5	0	66.6	0

TABLE XIII

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	Water	Mineral Oil	Glycerine	EHO
DMAEMA/EGDM	20/80	Hexane	0	58.3	66.7	58.3
DMAEMA/EGDM	40/60	Hexane	66.7	61.5	70.6	66.7
DMAEMA/EGDM	60/40	Hexane	77.3	61.5	72.2	76.2
DMAEMA/EGDM	80/20	Hexane	66.7	58.3	68.8	58.3
TBAEMA/EGDM	20/80	Hexane	0	70.6	75	70.6
TBAEMA/EGDM	40/60	Hexane	0	66.7	72.2	66.7
TBAEMA/EGDM	60/40	Hexane	0	61.5	68.75	61.5
TBAEMA/EGDM	80/20	Hexane	0	44.4	54.6	50
TBAEMA/EGDM	80/20	Hexane	54.6	54.6	58.3	50

TABLE XIV

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	Water	Mineral Oil	Glycerine	EHO
AMPS/EGDM	20/80	Xylene	84.3	83.3	85.3	83.3
BMA/EGDM	20/80	Hexane	0	70.6	75	68.8
BMA/EGDM	40/60	Hexane	0	70.6	77.3	70.6
BMA/EGDM	40/60	Ethyl-Alcohol	0	66.7	73.7	68.8
BMA/EGDM	60/40	Hexane	0	72.2	0	73.7
BMA/EGDM	80/20	Hexane	0	54.5	66.7	58.3

TABLE XV

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	Water	Mineral Oil	Glycerine	EHO
2 EHMA/EGDM	20/80	IPA	0	68.8	66.7	64.3
2 EHMA/EGDM	30/70	IPA	0	68.8	66.7	64.3
2 EHMA/EGDM	40/60	IPA	0	66.7	66.7	70.6
2 EHMA/EGDM	50/50	IPA	0	64.3	68.3	61.5
2 EHMA/EGDM	60/40	IPA	0	61.5	64.3	50
2 EHMA/EGDM	70/30	IPA	0	58.3	64.3	50
2 EHMA/EGDM	80/20	IPA	0	58.3	64.3	50

TABLE XVI

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	Water	Mineral Oil	Glycerine	EHO
MMA/EGDM	20/80	IPA	61.5	58.3	64.3	58.3
MMA/EGDM	30/70	IPA	64.3	61.5	66.7	61.5
MMA/EGDM	40/60	IPA	61.5	64.3	64.3	61.5
MMA/EGDM	50/50	IPA	58.3	54.5	61.5	58.3
MMA/EGDM	60/40	IPA	54.5	50	61.5	54.5
MMA/EGDM	70/30	IPA	66.7	61.5	72.2	64.3
MMA/EGDM	80/20	IPA	66.7	44.4	78.3	44.4

TABLE XVII

			Adsorption Capacity %
Monomers	Mole Ratio	Solvent	Water	PEG	Glycerine	EHO
HEMA/EGDM	20/80	IPA	54.5	54.5	54.5	50
HEMA/EGDM	30/70	IPA	58.3	64.3	58.3	54.5
HEMA/EGDM	40/60	IPA	58.3	61.5	64.3	54.5
HEMA/EGDM	50/50	IPA	61.5	61.5	61.5	50
HEMA/EGDM	60/40	IPA	61.5	64.3	61.5	50
HEMA/EGDM	70/30	IPA	58.3	64.3	58.3	50
HEMA/EGDM	80/20	IPA	61.5	58.3	61.5	54.5

The water adsorbing porous polymeric materials produced above in some instances are to be contrasted with the water containing beads of U.S. Patent No. 3,627,708, issued December 14, 1971. The bead of the '708 patent is produced by "in situ" suspension polymerization and is adapted to contain water only because of the presence of a solubilizer such as sodium bis(2-ethyl hexyl) sulfosuccinate. The materials of Example IV, on the other hand, are produced by a precipitation polymerization process, which contains no solubilizer and produces a material in the form of a powder consisting of unit particles, agglomerates and aggregates. Thus, these materials are very distinct from the materials of the '708 patent.
The particulates of the present invention can be used as a carrier and the particulate carrier means can be in the form of micron-sized beads or the particulate carrier means can be in the form of a powder. In the latter case, the powder constitutes a combined system of particles, the system of powder particles including unit particles of a size less than about one micron in average diameter, agglomerates of fused unit particles of sizes in the range of about twenty to about eighty microns in average diameter and aggregates of clusters of fused agglomerates of sizes in the range of about two hundred to about twelve hundred microns in average diameter.
As noted above, highly crosslinked, polymeric systems consisting of particles of submicron size, can be prepared from monomers having at least two polymerizable unsaturated bonds and containing no comonomers having monounsaturated moiety. These highly crosslinked systems can adsorb large quantities of active substances even of very different structures and properties.
Examples of such monomers are bis or poly acrylates, methacrylates or itaconates of ethylene glycol, propylene glycol, di-, tri-, tetra-, polyethylene glycol and propylene glycol, trimethylol propane, glycerine, erythritol, xylitol, pentaerythritol, di-pentaerythritol, sorbitol, mannitol, glucose, sucrose, cellulose, hydroxy cellulose, methyl cellulose and 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and cyclohexanediol and triol.
Similarly, bis acrylamido or methacrylamido compounds can be used, such as methylene bis acryl or methacrylamide, 1,2-dihydroxy ethylene bis-acryl or methacrylamide and hexamethylene bis-acryl or methacrylamide.
Another group of monomers are represented by di or poly vinyl esters such as divinyl oxalate, malonate, succinate glutarate, adipate, sebacate, divinyl maleate, fumarate, citraconate and mesaconate.
Still another group of monomers is represented by di or poly vinyl ethers of ethylene, propylene, butylene, glycols of glycerine, pentaerythritol, sorbitol, divinyl ether, di or polyallyl compounds based on glycols and glycerine or combinations of vinyl allyl or vinyl acryloyl compounds such as vinyl methacrylate, acrylate, allyl methacrylate, acrylate and methallyl methacrylate, acrylate.
Aromatic, cycloaliphatic or heterocyclic monomers such as divinyl benzene, toluene, diphenyl, cyclohexane, trivinyl benzene, divinyl pyridine and piperidine can also be used.
The polymerization is achieved by the use of a variety of free radical initiators which can be azo compounds, a peroxy dicarbonate, a peroxy ester or a sulfonyl acid peroxide. Illustrative of free radical initiators in the process are 2,2′-azobis(2,4-dimethyl-4-methoxy valeronitrile), benzoyl peroxide, 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, acetyl peroxide, 2-t-butylazo-2-cyano-4-methylpentane, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, diisononanyl peroxide, lauroyl peroxide, propinoyl peroxide, bis(4-t-butyl cyclohexyl) peroxy dicarbonate, di(sec-butyl) peroxy dicarbonate, diisopropyl peroxy carbonate, di(n-propyl) peroxy carbonate, di(2-ethylhexyl) peroxy carbonate, di(2-phenoxyethyl) peroxy carbonate, t-amyl peroxy pivatate, t-amyl perpivatate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy neodecanonate, t-amyl perneodecanonate, cumyl perneodecanonate, cumyl perpivate, 2,5-dimethyl-2,5-bis(2-ethyl hexanoyl peroxy) hexane, t-butylperoxy-2-ethylhexanoate, t-amyl peroxy (2-ethylhexanoate) and acetyl cyclohexyl sulfonyl peroxide.
Illustrative redox initiators are methylbutyl amine, bis(2-hydroxyethyl)butyl amine, butyldimethyl amine, dimethyl amine, dibenzylethyl amine, diethylmethyl amine, dimethylpentyl amine, diethyl amine, 2,2′,2˝-trihydroxy dipropyl ethyl amine, di-n-propylene amine, 2,2′,2˝-trimethyl tributyl amine, triethyl amine, dimethyl aminoacetal, pentylhexyl amine, triethanolamine, trihexyl amine, trimethyl amine, trioctadecyl amine, tripropyl amine, trisopropyl amine, tetramethylene diamine and esters of para-amino benzoic acid, e.g., p-dimethyl amino-2-ethylhexyl-benzoate, dimethyl aminoethyl acetate, 2-(n-butoxy)ethyl 4-dimethylaminobenzoate, 2-(dimethylamino) ethyl benzoate, ethyl-4-dimethylaminobenzoate, methyldiethanolamine, dibutyl amine, N,N-dimethylbenzylamine, methylethyl amine and dipentyl amine.

The following examples and tables illustrate the novel cleaning process of the present invention. Table XVIII lists a number of common stains and solvent or chemical treatments that may be empolyed to remove such stains in accordance with the present invention.

TABLE XVIII

STAIN	SOLVENT OR CHEMICAL TREATMENT
Tea	Ammonia
Coffee	Soap, dithionate
Cocoa	Soap, hydrocarbon emulsion
Chocolate	Soap, hydrocarbon emulsion
Milk, sour cream, yogurt	Hydrocarbon, ammonia
Beer	Acetic acid, hydrogen peroxide
Liquors	Enzyme, ammonia
Wine	Ammonia, alcohol, borax
Honey	Enzyme
Fruit juices	Enzyme, ammonia
Eggs	Water, soap, hydrocarbons
Red cabbage, beet root	Ammonia, dithionate
Vegetable and original oils	Organic solvents
Gravies	Hydrocarbon-emulsions, ammonia
Mustard	Glycerine, formic acid
Lipstick	Hydrocarbon emulsion, ethylalcohol
Various cosmetics	Ammonia, hydrocarbons, detergents
Nail lacquer	Butylacetate
Permanent wave	Hydrofluoric acid
Hair dyes	Citric acid, hydrofluoric acid
Henna	Glycerine
Fragrances	Hydrocarbon emulsion, alcohol
Toothpaste	Water
Castor Oil	Ethylalcohol, acetic acid
Fish oil	Hydrocarbon emulsion
Vaseline	Hydrocarbon, oxalic acid
Ointments	Hydrocarbons, acetic or formic acid
Iodine	Thiosulfate, hydrogen peroxide, acetic acid
Potassium hypermanganate	Sodium persulfite
Silver nitrate	Potassium iodide
Red or green ink	Gycerine, ammonia
Blue or black ink	Glycerine, ammonia, lacte, hydrofluoric acid
Rubber stamp ink	Glycerine and alcohol, hydrogen peroxide
Typing ribbon	Hydrocarbon emulsion
Nitrocellulose, cellulose acetate	Butlacetate, acetone, hydrocarbon
Vegetable adhesives	Ammonia, ethylalcohol, water
Photographic Developer	Thiosulfate, ammonia, hydrogen peroxide
Waxes, paraffin	Organic solvents
Fungus	Ammonia, hydrogen peroxide
Shoe polish	Hydrocarbon emulsion
Perspiration stains	Ammonia, acetic acid, ethylalcohol, hydrogen peroxide
Blood	Hydrogen peroxide, enzyme
Urine	Acetic acid
Rust	Oxalic acid, tin chloride
Grass, vegetables	Hydrocarbon emulsion, ethylalcohol

The disadvantage of conventional treatments is that the solvent dissolving the stain spreads, carrying the stain and depositing the diluted stain in the form of concentric rings. Thus, the textile has to be washed in the solvent to remove the stain entirely. When the macroporous copolymers of this invention are used as cleaning aids, this phenomena does not occur. Instead, the polymer adsorbs the dissolved stain leaving no concentric rings. After evaporation of the solvent from the polymer, the staining agent remains on the polymer. To complete the cleaning, the dry polymer is removed by brushing.
The copolymers can also be used to remove stains from solid substrates such as glass, metals, lacquers and wood, without using solvents or other chemicals which can cause deterioration of the substrate. Such treatment includes greasy and fatty viscous deposits. Simply dusting the deposit of vaseline or tar, followed by mixing and rubbing, removes the deposit as a plastic mass.

Example V

A cotton textile was stained with a drop of used motor oil and the oil was allowed to soak into the textile. The copolymer powder of Example I was mixed with heptane to a content of eighty percent by weight of the solvent. The copolymer powder containing the entrapped solvent was pressed onto the oil stained textile surface. The stain was absorbed into the powder within about five minutes and the powder was removed from the surface with a brush. No concentric rings were observed.

Example VI

Example V was repeated employing the copolymer powder of Example I produced with a polyunsaturated monomer of tetraethylene glycol dimethacrylate. Identical results were observed.

Example VII

Examples V and VI were repeated with a chlorophene solvent and identical results were observed.

Example VIII

Cotton, silk and artificial silk sample swatches were stained with strawberry jelly and sweet and sour sauce. The powder of Example I was mixed with twenty weight percent water solution of a nonionic surface active agent TRITON X-100. The powder was loaded to a content of about eighty weight percent of the solvent. The powder containing the entrapped solvent was pressed into each of the stained areas of the various swatches. At the end of five minutes, the powder was removed from each swatch with the assistance of pressurized air without a trace of concentric rings.

Example IX

Example VIII was repeated with the powder of Example VI containing eighty weight percent of water. Similar results were observed.

Example X

The powder of Example 1 was loaded with solvent and various stains and substrates were treated in accordance with the foregoing procedures. The solvents employed were heptane and methylene chloride. In each case, no rings were observed when the powder was removed from the sample surface being treated. The treated surfaces and the staining agents are shown below in Table XIX.

TABLE XIX

Stain	Surface
Butter	wool
Butter	paper
Mineral Oil	paper
Grass*	cotton
Used motor oil	wool
Used motor oil	silk
Used motor oil	rayon
Used motor oil	acetate silk
Used motor oil	linen
Used motor oil	nylon
Used motor oil	polyester 60%
	cotton 40%
Used motor oil	polyester 100%

*Ethyl.alcohol solvent

Example XI

A glass plate was covered with a silicone grease. The powder of Example I was dusted onto the plate and mixed with the grease. The powder absorbed the grease forming a plastic-like mass which was easily removed from the glass surface leaving a clean plate. Identical results were observed employing hydrocarbon greases and waxes.

Example XII

Spectacle lenses soiled by lipid deposits were cleaned in accordance with the procedure of Example XI. The lenses were flushed with water completely removing the lipid deposits from the surfaces of the spectacle lenses. Identical results were obtained employing the powder of Example VI. In either case, the powder did not adhere to the bifocal or trifocal lines of the spectacle lenses treated.

Example XIII

The powder of Example I and the powder of Example VI were used to clean dentures. Dentures covered by plaque were dusted with the powders, rubbed and flushed with water. In each case, the plaque was removed from the denture surfaces treated.
While the foregoing disclosure specifies various uses of the materials of the present invention, as well as various types and compositions of ingredients which may be entrapped within these and similar materials, the patent literature is replete with uses and ingredients which may be entrapped in these and similar materials. For example, U.S. Patent No. 4,690,825, discloses as active ingredients lubricants, emollients, moisturizers, pigments, insect or flea repellents, fragrances, vitamins and drugs. When the active ingredient is a drug, it is said to include anti-infectives such as antibiotics, fungicides, scabicides, pediculicides, iodine, anti-inflammatory agents, antipuritics, astringents, anti-hidrotics, keratolytic agents, caustics, keratoplastic agents, rubefacients, sunscreens, demukents, protectants and detergents. Uses of loaded beads includes cosmetic preparations such as hand creams, acne products, deodorants, antiperspirants, baby powders, foot powders, body powders, lip ices, lip sticks, baby creams and lotions, mouthwashes, dentifrices, medicated facial creams and lotions, shampoos, shaving creams, pre- and after-shave lotions, depilatories and hairgrooming preparations.
U.S. Patent No. 4,724,240, names as active ingredients ethylhexyl oxystearate, arachidyl propionate, ethylhexyl adipate, isopropyl myristate, ethanol, stearyl alcohol, propylene glycol, propionic acid, stearic acid, polyoxypropylene cetyl alcohol, carbowax, polyethylene glycol, petroleum jelly, mineral oil, mineral spirits, lanolin, acetylated lanolin, isopropyl lanolate, hexamethyldisiloxane, cyclic polydimethylsiloxanes, polyphenylmethylsiloxanes, polydimethyl-trimethylsiloxanes; phenyl, ethyl and vinyl-substituted polysilanes; and cosmetic dyes. Materials loaded with such ingredients are said to be useful in cosmetic, beauty, toiletry and healthcare products, insecticides, disinfectants, flavors, perfumes, antiperspirant wax or oil base sticks, deodorants, colognes, pressed powders and toilet soaps.
Entrapped functional materials in the Published European Application No. 0252463A2 are said to encompass pigments, perfumes, pheromones, synthetic insect attractants, pesticides including juvenile hormone analogs, herbicides, pharmaceuticals, antimicrobial agents, sunscreens, light stabilizers, fragrances, flavors including sweeteners and various chemicals. Of the various chemicals disclosed are menthol, soybean oil, Vitamin E, salicylic acid, squalane, simethicon, bromochlorinated paraffin, benzophenone, petroleum distillate, jojoba oil and citrus oil. The published application also specifically identifies and names four pheromones, twenty pesticides, twenty-three fragrances, about thirty-seven chemicals and some twenty-two emollients, that may be entrapped in the materials as active ingredients.
In the Patent Cooperation Treaty International Publication No. WO/88/01164, there is also listed as specifically named ingredients which may be loaded into the beads approximately twenty-two ultraviolet absorbers, nineteen insect repellants and thirty emollients. The publication also names several steroids including adrenocortical steroids such as fluocinolone, fluocinolone acetonide, triamcinolone acetonide, beta-methasone valerate, timobesone acetate, hydrocortisone, hydrocortisone acetate, triamcinolone, prednisolone, prednisolone acetate, dexamethasone, beclomethasone dipropionate, betamethasone diproprionate, betamethasone benzoate, clocorolone pivalate, halcinonide, flumethasone pivalate and desonide.
European Published Application No. 0306236A2, published March 3, 1989, discloses "in situ" and "post absorbed" suspension polymerized beads loaded with six different categories of active ingredients. The six categories of active ingredients are hair growth promoters, acne treatments, fragrances, vitamins, pain relievers and epidermal lipid substitutes. The hair growth promoter is Minoxidil. For acne treatment there is employed benzoyl peroxide, salicylic acid and resorcinol. Fragrances include flower oils, essential oils, animal and synthetic fragrances and resinoids. Some thirty-nine specific fragrances are named. Vitamins include A, D, E, K, B1, B2, B12, B15, B17, C, niacin, folic acid, panthotenic acid, biotin, bioflavinoids, choline, inositol and F. Cod liver oil and retinoids are also disclosed. Some twenty-two pain relievers and some twenty-two mixtures and combinations of various pain relievers are disclosed, among which are menthol, camphor and methyl salicylate. The epidermal lipid substitutes are squalane and squalene. The six categories of loaded beads may be used alone or as topical applications in creams, ointments, lotions and oils. In addition, the fragrance loaded beads can be added to perfumes, colognes, cosmetics, soaps, paper products, detergents and body and foot powders. The vitamin loaded beads also find application in lip balms, lipsticks, eye shadows, foundations and blushers.
In U.S. Patent No. 4,719,040, issued January 12, 1988, a porous polymer powder laden with perfume is included as an ingredient in an aqueous air freshener gel. U.S. Patent No. 4,764,362, issued August 16, 1988 and a divisional thereof U.S. Patent No. 4,813,976, issued March 21, 1989, relate to emery boards including an emollient entrapped onto an absorbent acrylates copolymer powder. Filing of a nail releases the emollient which conditions and lubricates the nails and cuticles. A toothpaste containing dental flossing tape is disclosed in U.S. Patent No. 4,776,358, issued October 11, 1988. Included as an ingredient of the dentifrice are "microsponges" containing a flavor oil. In U.S. Patent No. 4,828,342, issued May 9, 1989, copolymer bead and powder particles entrapping various functional materials are bonded to the surfaces of a reticulated polyurethane foam. Among the enumerated functional materials which may be entrapped are adhesives; pharmaceuticals such as insulin, interferon, albumin, hormones and monoclonal antibodies; flavors; fragrances for perfume samplers, air fresheners and drawer liners; colors; inks; liquid crystals; oils; waxes; solvents; resins; fire extinguishing agents; insect repellants for mothballs and flea and tick applications; agricultural chemicals such as insecticides, fungicides and pheromones; disinfectants; cosmetics such as skin lotions, hair care products, sunscreens and mouth wash; vitamins; antiperspirants; contraceptives; medicants such as Benzocaine, transdermal drugs, analgesics, allergy bacteria, methyl salicylate and nitroglycerin. Molded and layered articles are also disclosed.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods described herein without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are exemplary only and are not intended as limitations of the scope of the present invention.

Claims

1. A process of cleaning a surface soiled with a staining agent comprising applying to the soiled surface a highly cross-linked macroporous hydrophobic copolymer, the copolymer containing a chemical entrapped therein which is solvent for the staining agent present on the soiled surface, dissolving the staining agent with the solvent, absorbing the staining agent into the solvent entrapped copolymer and removing the copolymer containing the solvent and the dissolved staining agent from the surface.

2. A process of cleaning a surface soiled with a staining agent comprising applying to the soiled surface a highly cross-linked macroporous hydrophobic copolymer, rubbing and mixing the copolymer into the staining agent on the soiled surface, absorbing the staining agent into the copolymer and removing the copolymer containing the staining agent from the surface.